Polymerization catalyst and process



United States Patent 3,282,906 POLYMERIZATION CATALYST AND PROCESS John Boor, .lr., El Cerrito, Califi, assignor to Shell Oil Company, New York, N.Y., a corporation of Delaware No Drawing. Filed Sept. 17, 1962, Ser. No. 224,199 8 Claims. (Cl. 260-931) This invention relates to a new and improved method for the polymerization of alpha-olefins. More particularly, it relates to a novel catalyst combination for producing solid polyolefins, such as polypropylene.

In one aspect, this invention relates to a catalyst for the polymerization of olefins which comprises a novel combination of ingredients and which leads to the production of polyolefins of unusually high crystallinity or crystallizability and superior mechanical properties. In another aspect this invention is concerned with polypropylene of crystallinity higher than heretofore known.'

It is now well known that solid, linear polymers of alpha-olefins may be catalytically prepared at low temperatures and pressures. Such processes are conducted at temperatures ranging from about room temperature to about 150 C. and pressures below about 500 pounds per square inch. Broadly, suitable catalysts are formed from a transition metal compound and a metal organic compound capable of acting as a reducing agent.

The activity of these catalysts varies with the selection of proportions and combinations of compounds. The specific results of variations in catalyst composition are often unpredictable since relatively small changes can lead to widely different results in reaction rates and types of products.

Solid alpha-olefin polymers produced according to known methods with low pressure polymerization catalysts are characterized by a high degree of linearity and significant crystallizability of the polymer. A particularly useful olefin polymer is polypropylene. Although the catalysts of this invention can be utilized in producing various other polyolefins, the invention is of particular advantage in the production of polypropylene, and the discussion therefore will be mainly in terms of propylene polymerization.

A variety of results can be obtained in the low pressure polymerization of alpha-olefins with catalysts comprising a transition metal compound and a reducing agent, depending on the choice of the compound used as reducing agent, the choice of transition metal compound, and the choice of catalyst component ratios and reaction conditions. The reducing agents which are most widely used, particularly in stereoregular polymerization of propylene and higher alpha-olefins, are aluminum alkyl compounds, including aluminum trialkyls and aluminum alkyl halides.

Aluminum alkyl dihalides typically act quite dilferently in stereospecific catalyst compositions than aluminum trialkyls, aluminum dialkyl monohalides, and aluminum alkyl sesquihalides. It has been reported, for example, that a catalyst consisting merely of titanium trichloride and alkyl aluminum dichloride or dibromide does not permit the substantial conversion of propylene to high molecular weight solid crystalline polymer; 2,967,206 to Stuart et al. it is shown that such catalysts lead to the production of liquid polypropylene at condi-v tions at which use of aluminum dialkyl monochloride instead of aluminum alkyl dichloride leads to the production of crystalline solid polypropylene.

Coordination catalysts in which the reducing agent is aluminum ethyl dichloride can be made to catalyze the production of highly crystalline polypropylene when the catalyst composition is modified by the presence of certain selected compounds. Compoundswhich have been In US.

Patented Nov. 1, 1966 ,the formulas: P(O)Y PY RC(O)Y,

and R' Z wherein each Y is an alkylamino or alkoxy radical; Z is nitrogen, phosphorus, arsenic or antimony; R is an alkyl radical; R is a hydrogen, alkyl, aryl or aralkyl radical; and n is an integer from 1 to 4. Other compounds reported as effective are tertiary amines, pyridine and quaternary ammonium salts.

While the compounds which have been reported to effectively modify aluminum alkyl dihalides for the production of stereospecific alpha-olefin polymers have been characterized as electron donors it has been found that not by any means all compounds which can be classified as electron donors are effective to impart substantial activity and stereospecificity to a catalyst system in which an aluminum alkyl dihalide is the reducing agent. It has also been found that among effective compounds there is a great variation in the resulting molecular weight of the polymer produced at otherwise equal conditions.

It is an object of this invention to provide improved processes for the polymerization of alpha-monoolefins, and particularly propylene, to high molecular weight, highly crystalline polymers. A specific object of the invention is to provide an improved combination of catalytic ingredients to catalyze such polymerizations. Other objects will appear from the following description of this invention.

According to this invention alpha-olefins are polymerized to solid, linear polymers by contact with a catalyst formed by admixing 1) an aluminum hydrocarbyl dihalide having the formula RAIX wherein R is a hydrocarbon radical containing 1 to l2carbon atoms and selected from the group consisting of alkyl, aryl and aralkyl and X is ahalide, (2) a compound of a transition metal selected from the group consisting of titanium, zirconium,

vanadium, chromium, and molybdenum, said compound being selected from the group consisting of halides, alkoxyhalides, and acetylactonates, and (3) a third component which is a hydrocarbyl carbonate of the formula (R'O) C=O, wherein R is a hydrocarbon group of 1 to 10 carbon atoms, free of olefinic unsaturation.

The aluminum dihalides useful in this invention, when used either singly orin admixture with only a transition metal compound, are ineffective as catalysts for the production of high molecular weight alpha-olefin polymers of high crystallinity. The third components of the catalyst composition of this invention are also not effective catalysts of alpha-olefin polymerization.

The use of the highly stereospecific catalysts of this invention results in linear polymers of alpha-monoolefins of two or more carbon atoms. In general, suitable mono mers for the production of linear polyolefins are compounds having the formula RCH=CH wherein R is hy-. drogen or an aliphatic, cycloaliphatic or aromatic radical containing from 1 to 20 carbon atoms. Monomers in which R is an unbranched C or higher alkyl group generally result in polymers that are not crystallizable. Particularly suitable olefins for the production of crystallizable polymers are propylene, 1 butene, 3 methyl 1- butene, 4 methyl 1 pentene, 4 methyl 1 hexene and the like, which are known to produce stereoregular crystalline polymers. Other monomers which can be polymerized with such catalysts include styrene, allylbenzene, 4 phenyl l butene, 1 allyl naphthalene, 2 allyl toluene, vinyl cyclohexane, vinyl cyclohexene, l-alkenes of 5 and more carbon atoms, and cyclohexyl and aryl substituted l-alkenes. The catalysts may be used for the polymerization of mixtures of monomers when a crystalline product is possible and is desired.

One essential component of the catalyst compositions of this invention is a compound of a transition metal selected from the group consisting of titanium, zirconium, vanadium, chromium, and molybdenum. In the active catalyst the transition metal is at a valence below its maximum. Among the transition metal compounds that can be used are thehalides, :alkoxyhalides and acetylaoetonates of the named transition metals. Among the halides the order of preference runs from chlorides to bromides to iodides to fluorides.

Titanium trichloride is particularly preferred and especially the gamma form thereof. An active form of titanium trichlori'de is prepared, for example, by reducing titanium tetrachloride by reaction with an aluminum trialkyl, as described in US. 2,971,925 to Winkler et al. Activated forms of alpha and gamma titanium trichloride are sometimes referred to as delta titanium trichloride. The delta form, as Well as the beta form of titanium trichloride are also suitable for use in the catalysts of this invention.

Other suit-able titanium compounds include butoxy titanium dichloride, ethoxy titanium dichloride, and titanium acetylacetonate.

Similar compounds of zirconium, vanadium, chromium and molybdenum can be used, such as their trichlorides, tribromides, alkoxy dichlorides and acetylacetonate.

The reducing component of the catalyst is an aluminum alkyl di'halide of the formula RAlX wherein R isa hydrocarbon radical containing 1 to 2 carbon atoms, selected from the group consisting of alkyl, aryl, and aralkyl. Suitable hydrocarbon radicals include methyl, ethyl, propyl, butyl, phenyl, tolyl, phenylethyl, naphthyl and the like. The preferred halogens are chlorine and bromine. The preferred alkyl aluminum di'halides are the lower alkyl derivatives, i.e., those in which alkyl group has 1 to 4 carbon atoms. The most preferred is ethyl aluminum dichloride.

The third component of the catalyst composition is a hydrocarbyl carbonate which has the formula (RO) 0 0 wherein R is a hydrocarbon group of 1 to 10 carbon atoms free of olefinic unsaturation. In these compounds, R may be an alkyl, aryl, alkaryl, arlalkyl, cyclo- :alkyl,or alkyl substituted cycloalkyl group. A readily available and particularly preferred compound of this type is diethyl carbonate(C H O) C=O. Other suitable carbonates are dime-thyl carbonate, di-n-ptropy-l carbonate, diisobutyl carbon-ate, diisoamylcarb-onate, di-n-decyl carbonate, methyl ethyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditolyl carbonate, ethyl 'phenyl carbonate and the like.

For purposes of the present specification and claims, aryl is defined as a univalent hydrocarbon radical de rived from an unsaturated aromatic hydrocarbon by removal of a hydrogen from a carbon atom of an aromatic nucleus, as for example, phenyl or naphthyh Alkaryl radicals are alkyl radicals containing aryl substituent groups, as, for example, benzyl ,tolylmethyl, and the like.

The catalysts of this invention may be prepared by combining the ingredients in any desired order and contacting the combined ingredents wth the monomer to be polymerized. In a batch or .semibatch method, the catalyst ingredients are placed into a suitable hydrocarbon diluent in the reactor and monomer feed is then introduced. Additional catalyst component may he added during the course of the reaction. In continuous processes catalyst ingredients may be fed separately or in combination to the reactor as required during the course of the process.

Polymerization of alpha-monoolefins according to this invention and recovery of polymer are suitably carried out according to methods known to be suitable for low pressure olefin polymerization processes of the prior art. This includes bat-chwise, semibatchwise or continuous operations under conditions that exclude air and other atmospheric impurities, particularly moisture.

The reaction temperature is maintained between 0 and 150 C. and preferably between about 40 and about C. The pressure is not critical. It is usually only sufficient to maintain liquid phase reaction conditions; it may be autogenic pressure, which will vary depending upon the components of the reaction mixture and the temperature, or it may be higher, e.g., up to 1000 psi. High pressures-are suitably obtained by pressuring with monomer gas or with an inert gas.

In batch operations the polymerization time can be varied as desired; it may vary, for example, from a few minutes to several hours. Polymerization in batch processes may be terminated when monomer is no longer absorbed or earlier, if desired, e.g., if the reaction mixture becomes too viscous. polymerization mixture passes through a reactor of any suitable design. The polymerization reactions in such cases are suitably adjusted by varying the residence time. Residence times vary with the type of reactor system and range, for example, from 10 or 15 minutes to 1 or 2 hours.

In a suitable continuous operation, fresh feed, diluent and catalyst are continuously introduced into an agitated reaction zone, and reaction mixture slurry is withdrawn from the zone for removal and recovery of polymer. Heat of reaction may be withdrawn by indirect heat exchange or by evaporation of diluent and/or monomer in the reaction zone.

After the polymerization is complete, polymer is recovered from a slurry of the solid polymer in reaction diluent. A simple filtration is adequate to separate polymer from diluent. Other means for separating polymer from diluent may be employed. The polymer may be treated, separately or while slurried in the reaction mixture, in order to separate catalyst residues. Such treatment may be with alcohols such as methanol, acidified methanol, aqueous methanol, ethanol, isopropanol, and other similar polar liquids.

Catalysts may be used in a concentrattion ranging from about 0.1 to about 2% by weight based on the Weight of the reaction mixture. The concentration of monomer in the reaction mixture may vary upward from 5 percent by weight of the reaction mixture, depending on the conditions employed; the range from 20 to 80 percent by Weight is preferred.

The preferred molar ratios of aluminum compound to transition metal compound are in the range from 110.5 to 1:2. The amount of the third component is chosen in relation to the amount of aluminum compound present. The molar ratio of the third component to aluminum compound is below 1:1, and may be as low as 0.1:1. The preferred ratios are within the range of 0.4:1 to 08:1.

It is preferred to carry out the reaction according to this invention in a suitable diluent which is liquid under the conditions of reaction and relatively inert. The diluent may have the same number of carbon atoms per molecule as the olefin reactant or it may be in a different boiling range. Preferred as diluents are alkane and cycloalkane hydrocarbons. Suitable diluents are, for example, propane, butane, isobutane, n-pentane, isopentane, n-heptane, n-octane, isooctane, cyclohexane, methylcyclohexane, tetralin, decalin, or saturated hydrocarbon mixtures in the gasoline boiling range or diesel oil boiling range. Ar'omatichydrocarbons such as benzene, toluene, isopropylbenzene, xylene, or the like, or halogenated aromatic compounds such as chlorobenzene, or orthodichlorobenzene and the like may also be employed, if desired.

Although it is possible to use technical grades of olefins and diluents, containing the normal impurities present in such grades, it is much preferred to use purified olefin feed and purified diluents which are relatively free of impurities. Processes for purifying olefin reactants and diluents for low pressure polymerization processes are In continuous operations the I now well known to the art and are equally suitable for preparing feeds and diluents for use in processes of this invention.

In the examples and tables that follow, the intrinsic viscosity (I.V.) of polymers is determined from measurements of their specific viscosity in decalin at 150 C. The insolubles content is determined by the Soxhlet extraction of polymer in isoctane at its boiling point for 24 hours, using an extraction cycle of approximately 4 minutes. Parts and percentages in the examples are by weight unless otherwise stated.

Example 1 An active form of gamma titanium trichloride, for use in various polymerization experiments, is prepared by agitating a mixture of one mole of aluminum triethyl (AlEt and 3 moles of titanium tetrachloride in isopentane for one-half hour at 165 C. I

A small glass pressure vessel is carefully dried and purged with dry nitrogen. To the vessel there are added, in the absence of contact with air 5 ml. of purified heptane, 2.8 mmole (millimole) of aluminum ethyl dichloride (AlEtCI and 2.2 mmole of diethyl carbonate. The vessel is heated to 50? C. for A to /2 hour. Thereafter the vessel is cooled and 145 ml. of purified heptane, 1.1 mole of TiCl prepared as above, and about 20 g. of propylene, weighed exactly, are introduced into the vessel. The vessel is then sealed, brought to the desired reaction temperature of 50 C. in a constant temperature bath, and maintained under agitation for 20 hours. Eighty-two percent of the propylene is converted to solid polymer. Solid polymer is removed from the vessel and washed thoroughly with isopropyl alcohol. The polymer is inhibited against oxidative degradation by adding 0.2 by weight of a good phenolic antioxidant and is then dried in a vacuum oven at 50-60 C. for at least 20 hours. The polymer product has a high crystallinity, as indicated by the fact that 97% by weight is insoluble in boiling heptane. The crystalline melting point of the product is 162 C. and the I.V., measured in decalin, is 3.0 dl/ g.

Example 2 Example 1 is repeated, substituting di-n-propylcarbonate for the diethylcarbonate. The results are essentially identical. The insolubles content of the polymer is over 95%; the melting point is about 162 C.; and the I.V. in decalin is about 3 dl/g.

Example 3 When the reaction of Example 1 is carried out with a catalyst containing only gamma titanium trichloride and aluminum ethyl dichloride, only a very low conver sion of propylene to solid polypropylene is obtained.

Example 4 In the Examples 1 and 2, aluminum phenyl dichloride is substituted for aluminum ethyl dichloride. High conversion to highly crystalline polypropylene results.

Example 5 In Examples 1, 2, and 4, vanadium trichloride is substituted for titanium trichloride. Highly crystalline polypropylene is produced. Similar results are also obtained with trichl-orides of zirconium, molybdenum, and chromium.

Example 6 In Examples 1, 2, and 4, titanium ethoxy dichloride is substituted for titanium trichloride. Highly crystalline polypropylene is produced.

Example 7 Examples 1, 2, 4, 5, and 6 are repeated, substituting for diethyl carbonate di-n-propyl carbonate, diphenyl carbonate and ethyl phenyl carbonate in separate runs.

Similar good yields of highly crystalline polypropylene are obtained.

Example 8 The processes of Examples 1 and 2 are repeated, substituting 4-methy1-1-pentene for propylene. Highly crystalline poly-4-methyl-1-pentenes are recovered.

The catalyst system also permits the polymerization of ethylene, l-butene, 4-methyl-l-hexene, and the like to crystallizable polymers.

Solid polypropylenes of highly regular structure, such as isotactic and syndiotactic polypropylenes, are crystallizable, i.e., under suitable conditions of solidification they obtain a high degree of crystallinity as determined by X-ray analysis or comparable methods. In general, polypropylene having a crystallinity of at least about as measured by X-ray analysis, contains at most only a very small proportion of material which is extractable in boiling hydrocarbons, such as gasoline boiling range hydrocarbons. Typically the proportion of highly crystalline polypropylene which is extractable in boiling lheptane or isoctane is less than 10% and usually less than 5%. Conventional crystalline polypropylene has a viscosity average molecular weight of at. least about 40,000 and generally between 100,000 and 1,200,000. For convenience, the molecular weight is usually expressed in terms of intrinsic viscosity. The intrinsic viscosity of polypropylene, measured in decalin .at 150 C., is generally between 1.0 and 6 dl/ g. but may be as low as 0.5 or less and as high as 10 or more.

The process of this invention leads to the production of polyalpha-olefins of unusually high crystallinity. The polypropylene produced according to this invention is characterized by a crystalline melting point above C. and a high degree of insolubility in boiling heptane, e.g., above 95%. Its tensile strength is indicated by a tensile yield point (crosshead speed of 0.2"/min.) above 4900 p.s.i. at I.V.=2.2 (11/ g. The high stereoregularity of polypropylene produced according to this invention is shown by torsion pendulum crystallinities (calibrated with X-ray crystallinities above 72% at I.V.=2.2 dl/ g. Polypropylene produced with catalyst compositions according to this invention is characterized by a relatively low intrinsic viscosity, typically of the order of 3 dl/g., measured in 'decalin. Intrinsic viscosities in the range from 1.5 to 8 dl/ g. may be obtained, however, by utilizing molecular weight-modifying additives, such as hydrogen for molecular weight reduction, or by suitable changes in catalyst composition and reaction conditions.

Since the crystallinity of polypropylene produced according to this invention is higher than that of polypropylene produced with more conventional catalysts, it is found that the polymers of this invention have a higher tensile strength and greater stiffness. This improves their utility for numerous applications. In general, articles can be manufactured from these polymers by the same techniques utilized for polymers of somewhat lower crystallinity such 1 as are conventionally produced; these techniques include 1. A polymerization catalyst consisting essentially of an alkyl aluminum dichloride wherein the alkyl radicals contain 1 to 12 carbon atoms, titanium trichloride selected from the group consisting of the active alpha, beta, gamma and delta forms of titanium trichloride and a third compound having the formula (RO) C0, wherein R is an alkyl group of l to 10 carbon atoms, the molar ratio of said third compound to said aluminum dichloride being within the range of 0.1 :1 to 1:1.

2. A polymerization catalyst consisting essentially of ethyl aluminum dichloride, titanium trichloride selected from the group consisting of the active alpha, beta, gamma and delta forms of titanium trichloride, and diethyl carbonate, the molar ratio of ethyl aluminum dichloride to titanium trichloride being from 1:05 to 1:2 and that of diethyl carbonate to ethyl aluminum dichloride being from 0.4:1 to 08:1.

3. The catalyst of claim 2 wherein said titanium trichloride is beta titanium trichloride.

4. The catalyst of claim 2 wherein said titanium trichloride is gamma-titanium trichloride.

5. The catalyst of claim 2 wherein said titanium trichloride is delta-titanium trichloride.

6. In the polymerization of alpha-monoolefinic hydrocarbon material of 3 to 7 carbon atoms per molecule to form solid, crystallizable polymer, the improvement which comprises effecting the polymerization in liquid dispersion in hydrocarbon diluent and in the presence of a catalyst consisting essentially of an alkyl aluminum dichloride wherein the alkyl radicals contain 1 to 12 carbon atoms, titanium trichloride selected from the group consisting of the active alpha, beta, gamma and delta for-ms of titanium trichloride and a third compound having the formula (RO) C O wherein R is an alkyl group of 1 to 10 carbon atoms, the molar ratio of said third compound to said aluminum dichloride being with the range of 0.1:1 to 1:1.

7. The process according to claim 6 where said alphamonoolefinic hydrocarbon material is propylene.

8. In the polymerization of propylene to form solid,

References Cited by the Examiner UNITED STATES PATENTS 2,965,627 12/1960 Field et al 260-949 2,988,543 6/1961 Meyer et a1 26094.9 2,996,459 8/ 1961 Andersen et a1 260-949 3,149,097 9/1964 Coover et a1. 26094.9 3,230,208 1/ 1966 Coover et a1 260-93.7

JOSEPH L. SCHOFER, Primary Examiner. MORRIS LIEBMA'N, WILLIAM H. SHORT, Examiners.

F. M. SIKORA, M. B. KURTZMAN,

Assistant Examiners. 

6. IN THE POLYMERIZATION OF ALPHA-MONOOLEFINIC HYDROCARBON MATERIAL OF 3 TO 7 CARBON ATOMS PER MOLECULE TO FROM SOLID, CRYSTALLIZABLE POLYMER, THE IMPROVEMENT WHICH COMPRISES EFFECTING THE POLYMERIZATION IN LIQUID DISPERSION IN HYDROCARBON DILUENT AND IN THE PRESENCE OF A CATALYST CONSISTING ESSENTIALLY OF AN ALKYL ALUMINUM DICHLORIDE WHEREIN THE ALKYL RADICALS CONTAIN 1 TO 12 CARBON ATOMS, TITANIUM TRICHLORIDE SELECTED FROM THW FROUP CONSISTING OF THE ACTIVE ALPHA, BETA, GAMMA AND DELTA FORMS OF TITANIUM TRICHLORIDE AND A THIRD COMPOUND HAVING THE FORMULA (R''O)2CO WHEREIN R'' IS AN ALKYL GROJP OF 1 TO 10 CARBON ATOMS, THE MOLAR RATIO OF SAID THIRD COMPOUND TO SAID ALUMINUM DICHLORIDE BEING WITH THE RANGE OF 0.1:1 TO 1:1 